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Published January 15, 2021 | Supplemental Material + Submitted
Journal Article Open

Isolation and X-ray Crystal Structure of an Electrogenerated TEMPO–N₃ Charge-Transfer Complex


Advances in radical-based catalytic reactions have created a demand for understanding their mechanistic underpinnings. Here, we present the isolation, structural elucidation, and theoretical analysis of a catalytically relevant charge-transfer species formed between the azidyl radical and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). The unusual bond angles and pancake bonding between these two fragments highlight the weak bonding interactions present in this complex. This X-ray structure validates computational predictions as well as mechanistic proposals of TEMPO-mediated radical azidation reactions.

Additional Information

© 2021 American Chemical Society. Received 30 November 2020. Published online 6 January 2021. Published in issue 15 January 2021. Financial support was provided by National Science Foundation (CHE-1751839 to S.L.; CHE-1764328 to K.N.H.) and Bristol Myers Squibb (Unrestricted Grant in Organic Chemistry; H.M.N.). A.S. thanks the National Science Foundation for a Graduate Research Fellowship (DGE-1650604). The UCLA-DOE Institute's X-ray Crystallography Core Facility is supported by the U.S. Department of Energy (DE-FC02-02ER63421). The authors declare no competing financial interest. A previous version of this manuscript was deposited as a preprint in ChemRxiv (ref (26)). Accession Codes. CCDC 2035577 (1) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

Attached Files

Submitted - isolation-and-x-ray-crystal-structure-of-an-electrogenerated-tempo-n3-charge-transfer-complex.pdf

Supplemental Material - ol0c03966_si_001.pdf



Additional details

August 20, 2023
October 20, 2023